CN113929079B - Preparation method and application of biomass charcoal electrode - Google Patents
Preparation method and application of biomass charcoal electrode Download PDFInfo
- Publication number
- CN113929079B CN113929079B CN202111374268.8A CN202111374268A CN113929079B CN 113929079 B CN113929079 B CN 113929079B CN 202111374268 A CN202111374268 A CN 202111374268A CN 113929079 B CN113929079 B CN 113929079B
- Authority
- CN
- China
- Prior art keywords
- orange peel
- biomass charcoal
- electrode
- preset temperature
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The disclosure provides a preparation method and application of a biomass charcoal electrode, wherein the preparation method comprises the following steps: step S1: placing the orange peel into an oven for drying; step S2: loading the dried orange peel into a quartz boat and placing the quartz boat into a tube furnace, and carbonizing the quartz boat under inert gas, wherein the method comprises the following steps: step S2.1: setting a first heating rate to heat, and preheating for a first period of preset time at a first preset temperature when the temperature is raised to the first preset temperature; step S2.2: heating at a first heating rate to heat the material from a first preset temperature to a second preset temperature, and pyrolyzing the material at the second preset temperature for a second period of preset time to obtain the orange peel biomass charcoal electrode.
Description
Technical Field
The disclosure belongs to the technical field of biomass charcoal electrode preparation and electrochemical disinfection, and particularly relates to a preparation method and application of a biomass charcoal electrode.
Background
In recent years, along with the high-speed development of economy in China, the water pollution problem is increasingly serious, the water quality is in a worsening trend, and further, higher requirements are put forward on the water treatment process, especially the disinfection link. In face of the problems of disinfection byproducts and the limitation of microbial pathogen control generated by the current disinfection mode, the safe disinfection becomes an important research content for guaranteeing the life health of human beings and is an objective requirement for guaranteeing the safe drinking of water.
Chlorine has long been used as a disinfectant for most drinking water treatments due to its low transportation cost and good sterilizing effect, but chlorine itself is harmful to the human body and chlorine disinfection produces disinfection byproducts. The ozone disinfection has the characteristics of good effect, small dosage, quick action, few disinfection byproducts and simple production conditions, but the application of the ozone is limited because the ozone cannot be transported and stored for a long time and the ozone has no continuous disinfection effect. Ultraviolet rays are mainly sterilized through a physical process, and the sterilization effect of the ultraviolet rays is gradually weakened along with the increase of the turbidity of water and does not have continuous sterilization effect.
The electrochemical disinfection method has the characteristics of environmental friendliness, safety, high efficiency and low treatment cost, and is widely paid attention in recent years, but at present, the research level of electrochemical disinfection is still remained in the experimental exploration or demonstration engineering stage, the application of water treatment is influenced by various factors, the disinfection mechanism and the applicable conditions are not very clear, and the regulation and control rules of key disinfection species are still to be deeply researched. Currently, anodes for mainstream, efficient and stable electrochemical water treatment applications are still noble metal coated titanium electrodes, but the one-time investment cost of the treatment method is high. Biomass materials can be used not only to form biomass-derived carbon materials, but also to achieve doping of heteroatoms into the carbon network, particularly N-doping, which can improve the performance of the intended electrochemical device. Biomass has been used as a potential and successful raw material for preparing carbon and its composite-based materials to obtain lithium/sodium ion batteries of desirable properties as an inexpensive and abundant carbon source. However, the existing preparation method of the biomass material is complex and high in cost, and is rarely applied to water treatment disinfection, so that a simple, low-cost and large-scale preparation method is needed, and the method is widely applied to environmental treatment.
Disclosure of Invention
Aiming at the technical problems, the disclosure provides a preparation method and application of a biomass charcoal electrode, so as to at least partially solve the technical problems.
In order to solve the technical problems, an aspect of the present disclosure provides a method for preparing a biomass charcoal electrode, including:
step S1: placing the orange peel into an oven for drying;
step S2: loading the dried orange peel into a quartz boat, placing the quartz boat into a tube furnace, and carbonizing the quartz boat under inert gas, wherein the method comprises the following steps:
step S2.1: setting a first heating rate to heat, and preheating for a first period of preset time at a first preset temperature when the temperature is raised to the first preset temperature;
step S2.2: heating at the first heating rate to heat the biomass charcoal electrode from the first preset temperature to a second preset temperature, and pyrolyzing the biomass charcoal electrode at the second preset temperature for a second period of preset time to obtain the biomass charcoal electrode.
In one embodiment, in step S1, the size of the orange peel includes square small pieces with sides of 1-3 cm.
In one embodiment, in step S1, the temperature at which the orange peel is dried in the oven includes: the drying time is 60-100 ℃, and the drying time comprises: 24-36 h.
In one embodiment, in step S2, the inert gas includes: nitrogen or argon.
In one embodiment, in step S2.1, the first temperature increasing rate includes: 5-20 ℃/min.
In one embodiment, in step S2.1, the range of the first preset temperature includes: the first period of preset time at 80-100 ℃ comprises: 10-30 min.
In one embodiment, in step S2.2, the range of the second preset temperature includes: 600-800 ℃, and the second period of preset time comprises the following steps: and 1-3 h.
In another aspect of the present disclosure there is provided the use of a biomass charcoal electrode comprising: the biomass charcoal electrode prepared by the preparation method in the embodiment treats bacteria in water through electrochemical reaction.
In another embodiment, the electrolyte solution in the electrochemical reaction includes at least one of: sodium chloride solution, sodium sulfate solution, phosphate buffer solution.
In another embodiment thereof, the bacteria include at least one of the following: pseudomonas aeruginosa, pseudomonas stutzeri, and Escherichia coli.
From the above technical scheme, the preparation method and application of the biomass charcoal electrode disclosed by the disclosure have the beneficial effects that:
(1) According to the preparation method, the orange peel is placed into an oven to be dried, and moisture in the orange peel is removed; then, placing the dried orange peel into a tube furnace, and preheating for a first period of preset time at a first preset temperature to stabilize the temperature in the tube furnace and prevent the tube furnace from cracking due to excessively fast subsequent heating; then, the temperature in the tube furnace is raised from the first preset temperature to the second preset temperature, and pyrolyzed at the second preset temperature for a second preset time period, so that the orange Pi Tanhua in the tube furnace forms a small hole structure in the orange peel and a lasting freedom in the orange peel.
(2) The biomass charcoal electrode is prepared by utilizing the orange peel in the embodiment of the disclosure, and the method has the advantages of simple preparation method, easily obtained raw material orange peel, easy operation, no special equipment requirement, good reproducibility and capability of large-scale preparation.
(3) The biomass charcoal electrode prepared by the method in the embodiment of the disclosure contains a plurality of persistent free radicals; when the biomass charcoal electrode is used as a cathode, more superoxide radicals can be generated, and meanwhile, the anode can be promoted to generate more chlorine radicals.
Drawings
FIG. 1 is a front and back macroscopic state diagram of an orange peel biomass charcoal tablet in example 2 of the present disclosure;
FIGS. 2A to 2D are SEM (scanning electron microscope) images of orange peel biomass charcoal electrodes obtained in example 2 of the present disclosure at different magnifications;
FIGS. 3A-3D are SEM images of commercial graphite electrodes at various magnifications in an embodiment of the present disclosure;
FIG. 4 is an X-ray diffraction pattern of the orange peel biomass carbon electrode obtained in example 2 of the present disclosure;
FIG. 5 is a CuO/Cu contained in the orange peel biomass charcoal electrode obtained in example 2 of the present disclosure 2 Photoelectron spectrogram of O component on Cu2p orbit;
FIG. 6 is a CuO/Cu contained in an orange peel biomass charcoal electrode obtained in example 2 of the present disclosure 2 Photoelectron spectrogram of O component on Cu2p3 orbit;
FIG. 7 is an infrared spectrum characterization of the orange peel biomass charcoal electrode and graphite electrode obtained in example 2 of the present disclosure;
fig. 8 to 9 are graphs showing the effects of sterilization by orange peel biomass charcoal electrode and graphite electrode in examples 5 to 10 of the present disclosure;
FIG. 10 is a mechanism diagram of persistent radical generation in example 2 of the present disclosure;
FIG. 11 is a graph showing the results of surface persistent radical characterization of orange peel biomass charcoal electrodes and graphite electrodes obtained in example 2 of the present disclosure;
FIG. 12 is a graph of superoxide radical characterization results for orange peel biomass charcoal electrodes and graphite electrodes obtained in example 2 of the present disclosure;
fig. 13 is a graph of the results of chlorine radical characterization of orange peel biomass charcoal electrodes and graphite electrodes obtained in example 2 of the present disclosure.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The electrochemical disinfection and sterilization water treatment technology is a novel technology, has the characteristics of safety, high efficiency, convenience, flexibility, environmental friendliness and the like, and is receiving more and more attention.
The biomass charcoal electrode disclosed by the disclosure is simple in preparation method, easy to operate, free of special equipment requirements, green, safe, environment-friendly and good in reproducibility. Compared with other common electrodes, the biomass charcoal electrode prepared by the method is used for disinfection and sterilization in water treatment, and the electrode material with low disposable investment, low treatment cost and good sterilization effect is provided, so that a new application possibility is provided for the electrochemical disinfection technology in the requirements of safety terminal drinking water supply, small-scale emergency disinfection treatment, ecological facility water recycling and the like in areas without concentrated water supply.
The method takes orange peel as a raw material, utilizes high temperature to carbonize the orange peel into biomass-derived carbon, and utilizes CuO/Cu contained in the orange peel in the pyrolysis process 2 O reacts with organic functional groups on the surface of the orange peel to generate persistent free radicals. The biomass carbon sheet is used as an electrode of an electrochemical reaction device, and in the reaction process, the persistent free radical can induce oxygen and chloride ions in the solution to generate superoxide free radical and chloride free radical, so that sterilization of the saline water is realized.
The embodiment of the disclosure provides a preparation method of a biomass charcoal electrode, which comprises the following steps:
step S1: placing the orange peel into an oven for drying;
step S2: loading the dried orange peel into a quartz boat and placing the quartz boat into a tube furnace, and carbonizing the quartz boat under inert gas, wherein the method comprises the following steps:
step S2.1: setting a first heating rate to heat, and preheating for a first period of preset time at a first preset temperature when the temperature is raised to the first preset temperature;
step S2.2: heating at a first heating rate to heat the material from a first preset temperature to a second preset temperature, and pyrolyzing the material at the second preset temperature for a second period of preset time to obtain the orange peel biomass charcoal electrode.
Through the preparation method in the embodiment of the disclosure, firstly, the orange peel is put into an oven to be dried to remove the moisture in the orange peel; then, placing the dried orange peel into a tube furnace, and preheating for a first period of preset time at a first preset temperature to stabilize the temperature in the tube furnace and prevent the tube furnace from cracking due to excessively fast subsequent heating; then, the temperature in the tube furnace is raised from the first preset temperature to the second preset temperature, and pyrolyzed at the second preset temperature for a second preset time period, so that the orange Pi Tanhua in the tube furnace forms a small hole structure in the orange peel and a lasting freedom in the orange peel.
When the biomass charcoal electrode prepared by the preparation method in the embodiment of the disclosure is used as a cathode in electrochemical reaction, more superoxide radicals can be generated, more chlorine radicals can be generated at the anode, and bacteria can be inactivated when electrochemical disinfection is performed by utilizing abundant persistent free radicals contained in orange peels, so that the biomass charcoal electrode has a good disinfection effect.
According to the embodiment of the disclosure, in step S1, the size of the orange peel includes square small pieces with sides of 1-3 cm, and the sides of the orange peel can be selected from 1, 1.5, 2, 2.5, 3cm, etc.
According to the embodiment of the disclosure, orange peels cut into different sizes are cleaned with ultrapure water, and the orange Pi Yaping is washed with iron blocks; then, the cleaned orange peel is put into an oven for drying.
According to an embodiment of the present disclosure, in step S1, the temperature at which the orange peel is dried in the oven includes: 60-100 ℃, optionally 60, 70, 80, 90, 100 ℃, wherein 100 ℃ is preferred.
According to an embodiment of the present disclosure, orange peel drying time includes: 24-36 h, optionally 24, 26, 28, 30, 32, 34, 36h, of which 24h is preferred.
Through the embodiment of the disclosure, the moisture in the orange peel is primarily dried by the oven, so that the moisture residue in the orange peel can be reduced.
According to an embodiment of the present disclosure, in step S2, the inert gas includes: nitrogen, or argon, of which nitrogen is preferred.
According to the embodiment of the disclosure, the inert gas is used as the shielding gas, so that oxidation of the orange peel during carbonization in the tube furnace can be prevented, and nitrogen is selected as the shielding gas, so that the method is more economical.
According to an embodiment of the present disclosure, in step S2.1, the first temperature increase rate includes: 5-20 ℃/min, optionally 5, 10, 15, 20 ℃/min, preferably 10 ℃/min.
According to the embodiment of the disclosure, the temperature in the tube furnace is raised to the first preset temperature by using a temperature programming mode. ProgramThe heating rate is preferably 10 ℃/min, which is favorable for the slow temperature rise in the tube furnace, and the tube furnace is not damaged to burst; on the other hand, the formation of small pore structures inside the orange peel and the utilization of CuO/Cu existing in the orange peel itself are facilitated when sintering at a second preset temperature 2 The O component reacts with organic functional groups in the orange peel to generate persistent free radicals.
According to an embodiment of the present disclosure, in step S2.1, the range of the first preset temperature includes: 80-100 ℃, optionally 80, 90, 100 ℃, wherein 100 ℃ is preferred.
According to an embodiment of the present disclosure, in step S2.1, the first preset period of time includes: 10 to 30min, optionally 10, 15, 20, 25, 30min, preferably 20min.
According to the embodiment of the disclosure, the orange peel is dried in the oven at the temperature of 100 ℃ for 20min, the furnace tube is preheated, the working environment of the tubular furnace is kept stable, and the furnace tube of the tubular furnace is prevented from being burst from low temperature to high temperature.
According to an embodiment of the present disclosure, in step S2.2, the range of the second preset temperature includes: 600-800 ℃, optionally 600, 650, 700, 750, 800 ℃, with 700 being preferred.
According to an embodiment of the present disclosure, in step S2.2, the second preset period of time includes: 1 to 3 hours, optionally 1, 1.5, 2, 2.5, 3 hours, of which 2 hours are preferred.
According to the embodiment of the disclosure, the orange peel is sintered at the second preset temperature, so that on one hand, the surface of the orange peel is carbonized and a small hole structure is formed inside the orange peel; on the other hand, cuO/Cu which is beneficial to the existence of orange peel 2 O reacts with organic functional groups in the orange peel to generate persistent free radicals.
In order to make the objects, technical schemes and advantages of the present disclosure more apparent, a method for preparing a biomass charcoal electrode is disclosed in further detail in the following with reference to specific examples.
Example 1
The peel obtained from the market is cut into small pieces with a side length of 2 x 2cm, washed clean with ultrapure water and flattened with iron pieces. Next, the orange peel was baked in an oven at 80℃for 36h. Then, taking out and putting the quartz boat into a tubular graphite furnace, heating the quartz boat at a first heating rate of 10 ℃/min, heating the quartz boat to a first preset temperature of 100 ℃, and maintaining the quartz boat at the first preset temperature for 20min. Then, the temperature is increased to 700 ℃ at the temperature rising rate of 10 ℃/min, and the temperature is maintained for 2 hours, so that the formed biomass charcoal electrode slice is finally obtained.
The specific surface area of the orange peel was measured to be 3.80m by a specific surface area meter 2 And/g, measuring the pore diameter of the orange peel by using a scanning electron microscope to be about 20 mu m.
Example 2
Orange peel obtained from the market was cut into small pieces with a side length of 2.5X2.5 cm, washed clean with ultrapure water, and then flattened with iron pieces. Next, the orange peel was baked in an oven at 100deg.C for 24 hours. Then, taking out and putting the quartz boat into a tubular graphite furnace, heating the quartz boat at a first heating rate of 10 ℃/min, heating the quartz boat to a first preset temperature of 100 ℃, and maintaining the quartz boat at the first preset temperature for 20min. Then, the temperature is increased to 700 ℃ at a heating rate of 10 ℃/min, and the temperature is maintained for 2 hours, so that the formed biomass charcoal electrode slice is finally obtained (figure 1).
The specific surface area of the orange peel was measured to be 3.80m by a specific surface area meter 2 And/g, measuring the pore diameter of the orange peel by using a scanning electron microscope to be about 20 mu m.
Fig. 1 is a front and back macroscopic state diagram of an orange peel biomass charcoal tablet in example 2 of the present disclosure.
As shown in FIG. 1, the surface of the obtained orange peel biomass charcoal tablet has fine pores formed.
Example 3
Orange peel obtained from the market was cut into small pieces with a side length of 2.5X2.5 cm, washed clean with ultrapure water, and then flattened with iron pieces. Next, the orange peel was baked in an oven at 100deg.C for 24 hours. Then, taking out and putting the quartz boat into a tubular graphite furnace, heating the quartz boat at a first heating rate of 20 ℃/min, heating the quartz boat to a first preset temperature of 100 ℃, and maintaining the quartz boat at the first preset temperature for 20min. Then, the temperature is increased to a second preset temperature of 800 ℃ at a heating rate of 20 ℃/min, and the temperature is maintained for 2 hours, so that the formed biomass charcoal electrode slice is finally obtained.
The specific surface area of the orange peel was measured to be 4.92m by a specific surface area meter 2 And/g, measuring the pore diameter of the orange peel by using a scanning electron microscope to be about 15 mu m.
Example 4
Orange peel obtained from the market was cut into small pieces with a side length of 2.5X2.5 cm, washed clean with ultrapure water, and then flattened with iron pieces. Next, the orange peel was baked in an oven at 100deg.C for 24 hours. Then, taking out and putting the quartz boat into a tubular graphite furnace, heating the quartz boat at a first heating rate of 10 ℃/min, heating the quartz boat to a first preset temperature of 100 ℃, and maintaining the quartz boat at the first preset temperature for 20min. Then, the temperature is increased to a second preset temperature of 800 ℃ at a heating rate of 10 ℃/min, and the temperature is maintained for 2 hours, so that the formed biomass charcoal electrode slice is finally obtained.
The specific surface area of the orange peel measured by a specific surface area measuring instrument is 5.01m 2 And/g, measuring the pore diameter of the orange peel by using a scanning electron microscope to be about 15 mu m.
Characterization test
The fired orange peel biomass charcoal electrode of example 2 was characterized.
Fig. 2A to 2D are SEM images of orange peel biomass charcoal electrodes obtained in example 2 of the present disclosure at different magnifications.
As shown in FIGS. 2A to 2D, the surface of the orange peel was observed to have a large number of pores continuously distributed by a scanning electron microscope, and the pore diameter of the orange peel was measured to be about 20 μm by a scanning electron microscope.
Commercial graphite electrodes are widely used in electrochemical reactions because of their good electrical conductivity.
Fig. 3A-3D are SEM images of commercial graphite electrodes at different magnifications in an embodiment of the present disclosure.
As shown in figures 3A to 3D,the surface of the commercial graphite electrode is compact, the aperture is smaller, the aperture of the graphite electrode is about 5 mu m measured by a scanning electron microscope, and the specific surface area of the commercial graphite electrode is 6.9m measured by a specific surface determinator 2 And/g. Compared with a commodity graphite electrode, the orange peel biomass charcoal electrode prepared by the method in the embodiment 2 has larger aperture and smaller specific surface area, and the aperture structure is favorable for electron transmission and has better disinfection and sterilization effect in the disinfection and sterilization process.
Fig. 4 is an X-ray diffraction pattern of copper oxide crystals of the orange peel biomass carbon electrode obtained in example 2 of the present disclosure.
As shown in FIG. 4, it was confirmed by XRD test that the orange peel contained a small amount of Cu, and that Cu was present in the form of CuO/Cu 2 O components are matched, and the JCPLDS card number of CuO is: no.00-048-1548.
FIG. 5 is a CuO/Cu contained in an orange peel biomass charcoal electrode obtained in example 2 of the present disclosure 2 Photoelectron spectrogram of O component on Cu2p orbit; FIG. 6 is a CuO/Cu contained in an orange peel biomass charcoal electrode obtained in example 2 of the present disclosure 2 Photoelectron spectrum of O component on Cu2p3 orbit.
As shown in FIGS. 5 to 6, by analyzing the valence state of the Cu-containing component of the orange peel biomass charcoal electrode, it was confirmed that Cu in the orange peel biomass charcoal electrode was in CuO/Cu 2 O exists in the form of a ring. Due to CuO/Cu in orange peel 2 O reacts with functional groups having aromatic structures in the orange peel, biopolymers, and the like during firing to generate persistent radicals.
Fig. 7 is an infrared spectrum characterization diagram of the orange peel biomass charcoal electrode and graphite electrode obtained in example 2 of the present disclosure.
As shown in fig. 7, by infrared spectroscopic testing of the orange peel biomass charcoal electrode and graphite electrode, it was found that c=c-C, N (CH 3 ) 2 Structure (aromatic I, aromatic II) and CH in biopolymer 2 The structure (biopolymer I, biopolymer II) is present, while the main part in the graphite electrodeThe component is biopolymer II such as petroleum coke and needle coke, and almost no aromatic substances are contained.
The embodiment of the disclosure also provides a biomass carbon sheet prepared by the preparation method, wherein the biomass carbon sheet is used as an electrode (cathode or anode) to realize disinfection and sterilization of water through electrochemical reaction.
According to an embodiment of the present disclosure, the electrolyte solution of the electrochemical reaction species includes at least one of: sodium chloride solution, sodium sulfate solution, phosphate Buffered Saline (PBS).
According to an embodiment of the present disclosure, the bacteria include at least one of: pseudomonas aeruginosa, pseudomonas stutzeri, and Escherichia coli.
Example 5
The orange peel biomass charcoal electrode prepared by the method of example 2 is used as a cathode, an iridium oxide/ruthenium oxide coating titanium electrode is used as an anode, and the two electrodes are inserted into an electrolytic cell containing pseudomonas stutzeri, wherein electrolyte solution is 0.09% sodium chloride solution, the two electrode plates are connected with an electrochemical workstation by a lead, and a 10V direct current voltage is introduced for electrochemical disinfection and sterilization test.
Example 6
The process in example 6 is the same as that in example 5, except that the cathode electrode employed in example 6 is a graphite electrode.
Example 7
The process in example 7 is the same as that in example 5, except that the electrolyte solution used in example 7 is a 0.09% sodium sulfate solution.
Example 8
The process in example 8 is the same as that in example 7, except that the cathode electrode employed in example 8 is a graphite electrode.
Example 9
The procedure in example 9 was the same as in example 5, except that the electrolyte solution used in example 9 was phosphate buffer solution (containing 0.09% sodium chloride).
Example 10
The process in example 10 is the same as that in example 9, except that the cathode electrode employed in example 10 is a graphite electrode.
Fig. 8 to 9 are graphs showing the effect of sterilizing with the orange peel biomass charcoal electrode and the graphite electrode in examples 5 to 10 of the present disclosure.
As shown in fig. 8 to 9, when the electrochemical sterilization reaction is performed by selecting the orange peel biomass charcoal electrode as the cathode, the sterilization effect by the sodium chloride electrolyte solution is the best regardless of whether the electrochemical sterilization is performed by the phosphate buffer solution (containing 0.09% sodium chloride), the 0.09% sodium chloride solution, or the 0.09% sodium sulfate solution. When 0.09% sodium chloride is used as electrolyte solution and the orange peel biomass charcoal electrode or the graphite electrode is used as a cathode, the disinfection and sterilization effect of the orange peel biomass charcoal electrode used as the cathode is better than that of a commercial graphite electrode.
Fig. 10 is a mechanism diagram of persistent radical generation in example 2 of the present disclosure.
As shown in FIG. 10, the biomass charcoal electrode contains CuO/Cu in the orange peel during firing 2 O component, aromatic molecular precursor (phenol or chlorobenzene, X in FIG. 10 is halogen atom or-OH) containing benzene ring is adsorbed on the surface of copper oxide particles by physical adsorption at high temperature, then chemical reaction is carried out by dehydration or HX removal to transfer electrons to Cu (II), reduce Cu (II) to Cu (I), and simultaneously generate a plurality of permanent radical species (PFR) of which carbon is adjacent to one oxygen atom and oxygen is mixed with semi-quinoid radical and methoxybenzene radical of a central structure ·﹣ )。
Fig. 11 is a graph showing the results of surface persistent radical characterization of the orange peel biomass charcoal electrode and graphite electrode obtained in example 2 of the present disclosure.
As shown in fig. 11, the characteristic peak intensity of the persistent radical contained in the orange peel biomass charcoal electrode before the reaction was higher than that of the persistent radical and graphite electrode contained in the biomass charcoal electrode after the reaction, demonstrating that the persistent radical was consumed for killing bacteria. It can also be seen from fig. 11 that the graphite electrode contains little persistent radicals in the embodiments of the present disclosure. It is also proved by the above that the electrochemical disinfection and sterilization effect is stronger when the orange peel biomass charcoal electrode is selected as the cathode than when the graphite electrode is selected as the cathode. Embodiments of the present disclosure employ electron spin resonance spectroscopy (ESR, BRUKER EMX, germany) for relevant radical tests.
In the electrochemical disinfection and sterilization process, the selected orange peel biomass charcoal electrode can induce the generation of superoxide radicals by the durable free radicals, and the reaction involved in the reaction process is as follows:
O 2 +PFR ·﹣ →O 2 ·﹣ +PFR(1)
fig. 12 is a graph showing superoxide radical characterization results of the orange peel biomass charcoal electrode and graphite electrode obtained in example 2 of the present disclosure.
As shown in fig. 12, in the disinfection and sterilization process using the orange peel biomass charcoal electrode, the amount of the generated superoxide radical induced by the persistent free radical is the greatest, and the superoxide radical has stronger oxidizing property, so that the disinfection and sterilization effect of the orange peel biomass charcoal electrode is stronger than that of the graphite electrode, and the test using the sodium sulfate solution is performed to reduce the interference of the sodium chloride solution and the phosphate solution (containing sodium chloride solution) on the detection of the superoxide radical.
In the electrochemical disinfection and sterilization process, the orange peel biomass charcoal electrode is more beneficial to the generation of chlorine free radicals and free chlorine induced by the ruthenium iridium coating titanium anode compared with a graphite electrode, and the reaction involved in the reaction process is as follows:
MO X +Cl ﹣ +hv→Cl · (2)
Cl · +Cl ﹣ →Cl 2 +e - (3)
Cl · +Cl ﹣ →Cl 2 (4)
Cl 2 +H 2 O→HOCl+H + +Cl ﹣ (5)
wherein MO is X Refers to a metal oxide anode, herein referred to as an iridium oxide/ruthenium oxide coated titanium electrode.
Fig. 13 is a graph of the results of chlorine radical characterization of orange peel biomass charcoal electrodes and graphite electrodes obtained in example 2 of the present disclosure.
As shown in fig. 13, the orange peel biomass charcoal electrode produced more chlorine radicals than the graphite electrode; and the electronegativity of the orange peel biomass charcoal electrode is stronger than that of the graphite electrode, and bacteria can be combined with the surface of the anode through larger repulsive force, so that the bacteria are inactivated by chlorine radicals, and the orange peel biomass charcoal electrode has a higher sterilization effect.
In the embodiments of the present disclosure, the orange peel biomass carbon electrode is substantially free of persistent radicals, which in turn may substantially induce the production of superoxide radicals and chloride radicals. Radical species (superoxide radicals and chlorine radicals) can rob other electrons because of containing unpaired electrons, can oxidize biological cells (bacteria) near the electrode to lose electrons, destroy DNA double-chain or single-chain structures in the bacterial cells, deactivate the bacteria and finally cause cell damage apoptosis. The graphite electrode does not contain persistent free radicals, and the graphite electrode can not induce the generation of superoxide radicals and chlorine radicals in a large quantity, so that the sterilizing effect is lower than that of the orange peel biomass charcoal electrode when the graphite electrode is selected as a cathode.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (9)
1. An application of biomass charcoal electrode disinfection and sterilization, comprising:
the biomass charcoal electrode is used as a cathode of an electrochemical reaction, and the bacteria in water are treated by utilizing persistent free radicals contained in the biomass charcoal electrode and generating superoxide free radicals through the electrochemical reaction and promoting the anode to generate chlorine free radicals;
the preparation method of the biomass charcoal electrode comprises the following steps:
step S1: placing the orange peel into an oven for drying;
step S2: loading the dried orange peel into a quartz boat, placing the quartz boat into a tube furnace, and carbonizing the quartz boat under inert gas, wherein the method comprises the following steps:
step S2.1: setting a first heating rate to heat, and preheating for a first period of preset time at a first preset temperature when the temperature is raised to the first preset temperature;
step S2.2: heating at the first heating rate to heat the orange peel from the first preset temperature to a second preset temperature, and pyrolyzing the orange peel at the second preset temperature for a second preset time to utilize CuO/Cu contained in the orange peel during pyrolysis 2 And (3) reacting the O with organic functional groups on the surface of the orange peel to generate persistent free radicals, thereby obtaining the orange peel biomass charcoal electrode.
2. The use according to claim 1, wherein in step S1, the peel size is a square piece with a side length of 1-3 cm.
3. Use according to claim 1, wherein in step S1, the orange peel is dried in an oven at a temperature of: the drying time is 60-100 ℃, and the drying time is as follows: 24-36 h.
4. The use according to claim 1, wherein in step S2, the inert gas is: argon gas.
5. The use according to claim 1, wherein in step S2.1, the first rate of temperature increase is: 5-20 ℃/min.
6. The use according to claim 1, wherein in step S2.1, the first preset temperature ranges from: 80-100 ℃, wherein the first period of preset time is as follows: 10-30 min.
7. The use according to claim 1, wherein in step S2.2, the second preset temperature ranges from: 600-800 ℃, and the second period of preset time is as follows: and 1-3 h.
8. The use according to claim 1, wherein the electrolyte solution in the electrochemical reaction is one of a sodium chloride solution, a sodium sulfate solution, a phosphate buffer solution.
9. The use according to claim 1, wherein the bacterium is one of pseudomonas aeruginosa, pseudomonas stutzeri, escherichia coli.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111374268.8A CN113929079B (en) | 2021-11-19 | 2021-11-19 | Preparation method and application of biomass charcoal electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111374268.8A CN113929079B (en) | 2021-11-19 | 2021-11-19 | Preparation method and application of biomass charcoal electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929079A CN113929079A (en) | 2022-01-14 |
| CN113929079B true CN113929079B (en) | 2023-08-22 |
Family
ID=79287448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111374268.8A Active CN113929079B (en) | 2021-11-19 | 2021-11-19 | Preparation method and application of biomass charcoal electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929079B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114984912A (en) * | 2022-06-20 | 2022-09-02 | 中国科学院生态环境研究中心 | Method for preparing biomass charcoal material from pericarp of citrus |
| CN115304050B (en) * | 2022-08-12 | 2024-01-23 | 云南师范大学 | Preparation method of citrus peel biochar and application of citrus peel biochar in aspect of wastewater treatment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012125839A1 (en) * | 2011-03-15 | 2012-09-20 | University Of Kentucky Research Foundation | Carbon particles |
| CN107021483A (en) * | 2017-05-31 | 2017-08-08 | 宁夏大学 | A kind of method based on biomass by hydro-thermal synthesizing flaky porous carbon |
| CN109019552A (en) * | 2018-07-17 | 2018-12-18 | 武汉大学 | A kind of alkali metal ion secondary cell biomass carbon negative electrode material and preparation method |
| CN109850867A (en) * | 2019-02-12 | 2019-06-07 | 中国环境科学研究院 | A kind of preparation method of biomass carbon |
| CN111906138A (en) * | 2020-08-04 | 2020-11-10 | 昆明理工大学 | Method for degrading organic pollutants based on biochar |
| CN113178589A (en) * | 2021-04-12 | 2021-07-27 | 武汉氢能与燃料电池产业技术研究院有限公司 | Microbial fuel cell cathode, preparation method thereof and microbial fuel cell |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014154225A (en) * | 2013-02-05 | 2014-08-25 | Sony Corp | Electrode material, electrode, and battery |
| KR102506938B1 (en) * | 2018-02-02 | 2023-03-07 | 현대자동차 주식회사 | Method for manufacturing activated carbon |
-
2021
- 2021-11-19 CN CN202111374268.8A patent/CN113929079B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012125839A1 (en) * | 2011-03-15 | 2012-09-20 | University Of Kentucky Research Foundation | Carbon particles |
| CN107021483A (en) * | 2017-05-31 | 2017-08-08 | 宁夏大学 | A kind of method based on biomass by hydro-thermal synthesizing flaky porous carbon |
| CN109019552A (en) * | 2018-07-17 | 2018-12-18 | 武汉大学 | A kind of alkali metal ion secondary cell biomass carbon negative electrode material and preparation method |
| CN109850867A (en) * | 2019-02-12 | 2019-06-07 | 中国环境科学研究院 | A kind of preparation method of biomass carbon |
| CN111906138A (en) * | 2020-08-04 | 2020-11-10 | 昆明理工大学 | Method for degrading organic pollutants based on biochar |
| CN113178589A (en) * | 2021-04-12 | 2021-07-27 | 武汉氢能与燃料电池产业技术研究院有限公司 | Microbial fuel cell cathode, preparation method thereof and microbial fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| Yang,Y.Insights into the mechanism of enhanced photocatalytic dye degradation and antibacterial activity over ternary zno/znse/mose2 photocatalysts under visible light irradiation.APPLIED SURFACE SCIENCE.2021,第539卷全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929079A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113929079B (en) | Preparation method and application of biomass charcoal electrode | |
| Huo et al. | A Cu 3 P nanowire enabling high-efficiency, reliable, and energy-efficient low-voltage electroporation-inactivation of pathogens in water | |
| Yang et al. | Boosting power density of microbial fuel cells with 3D nitrogen‐doped graphene aerogel electrode | |
| Long et al. | Enhancement of azo dye degradation and power generation in a photoelectrocatalytic microbial fuel cell by simple cathodic reduction on titania nanotube arrays electrode | |
| Zhu et al. | Improved performance of membrane free single-chamber air-cathode microbial fuel cells with nitric acid and ethylenediamine surface modified activated carbon fiber felt anodes | |
| CN111389364B (en) | Bone charcoal capable of efficiently oxidizing trivalent arsenic in water and application thereof | |
| CN107601566B (en) | A method of there is the amorphous oxide molybdenum quantum dot of LSPR effect using the preparation of ontology molybdenum disulfide | |
| Hu et al. | Resolving the Tribo-catalytic reaction mechanism for biochar regulated Zinc Oxide and its application in protein transformation | |
| CN107010622A (en) | Medium barrier plasma is modified microwave activation lignin-base carbon resistance rod preparation method | |
| CN112076759A (en) | Graphite felt cathode, preparation method and application thereof | |
| Hu et al. | Atomic Ti-Nx sites with switchable coordination number for enhanced visible-light photocatalytic water disinfection | |
| CN115092994B (en) | Method for removing phosphate ions in water by using capacitive deionization composite electrode containing electron shuttle | |
| CN114917910B (en) | Preparation method and application of cobalt oxide deposited alkali modified sludge biochar catalyst | |
| CN111003760A (en) | Preparation method of photoelectrocatalysis anode material with TNTs as substrate | |
| KR102029539B1 (en) | Method of manufacturing electrode for water treatment | |
| JP2017154081A (en) | Catalyst composition, electrode for organic wastewater treatment device, and organic wastewater treatment device | |
| CN109796014A (en) | It is a kind of using ferric nitrate as the preparation method of the mesoporous activated carbon of activator | |
| CN114426320A (en) | Preparation method of FeOCl/nitrogen-phosphorus self-doped biochar cathode and application of FeOCl/nitrogen-phosphorus self-doped biochar cathode in sewage treatment | |
| CN109686987B (en) | Carbon/nitrogen-loaded titanium dioxide nanotube matrix and application thereof in microbial fuel cell | |
| CN113003668B (en) | Method for synchronously removing PPCPs (pentatricopeptide repeats) by inactivating urine by using singlet oxygen generated in situ by three-dimensional electrochemical reactor | |
| Luo et al. | Defective nitrogen doped carbon material derived from nano-ZIF-8 for enhanced in-situ H2O2 generation and tetracycline hydrochloride degradation in electro-Fenton system | |
| Zhang et al. | A carbon membrane-mediated CdSe and TiO 2 nanofiber film for enhanced photoelectrochemical degradation of methylene blue | |
| JP4001673B2 (en) | Porous carbon electrode for water treatment | |
| Peng et al. | Assessing the potential of biochar derived from sewage sludge for photoelectrode fabrication: methods, mechanisms, and conclusions | |
| CN114628707A (en) | Modified carbon brush cathode material for microbial electro-Fenton fuel cell and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |